Thin film catalyst manufacturing apparatus and manufacturing method

Abstract

The present invention provides a manufacturing apparatus and a manufacturing method for a thin film catalyst. The manufacturing apparatus includes a vacuum chamber, a plurality of evaporators, a plurality of gas introduction tubes, an ion generator, and a control unit. The plurality of evaporators evaporate at least one film-forming material. The plurality of gas introduction tubes supply reactive gases. The ion generator ionizes the reactive gas and the evaporated film-forming material. The control unit controls the vacuum chamber to perform vacuum suction, starts at least two of the plurality of evaporators, controls the gas introduction tube to supply reactive gases, and controls and adjusts the magnitude of the ion source current of the ion generator to react the evaporated film-forming material with the reactive gas to deposit a catalyst film on the surface of the substrate. The present invention solves the problems existing in the conventional manufacturing technology for manufacturing high-entropy alloy thin films and multi-metallic element ceramic thin film catalysts, such as low manufacturing efficiency, long film-forming time, high cost, serious pollution, and difficulty in large-scale industrial production.

Description

[Technical field]

[0001] The present invention relates to the technical field of catalysts, and in particular to an apparatus and method for producing thin film catalysts. [Background technology]

[0002] With the development of industrial technology, catalysts, known as the "foundation of modern industry," play an important role in various fields of production and environmental protection. More than 80% of chemical processes among them use heterogeneous catalysts, mainly supported metal catalysts. Supported catalysts have a very wide range of applications and play an irreplaceable role in the realization of ammonia synthesis, conversion of carbon-based resources, fine chemical industry, pollution treatment, drug synthesis, new energy battery membranes, etc. Existing preparation processes for mass production of catalysts, such as the immersion method, co-precipitation method, and ion exchange method, have serious pollution, are difficult to control the impurity content, and cannot fully control the stability (including high temperature stability) and reproducibility.

[0003] In addition, research has shown that medium and high entropy alloy catalysts and multi-metal element ceramic membrane catalysts have a high degree of formulation freedom, and the lattice distortion optimizes the electronic structure of the active site. In addition, high entropy alloy and multi-metal element ceramic membrane catalysts can maintain the relative stability of a single-phase structure in high temperature and corrosive application environments due to the hysteresis diffusion effect, and can maintain thermodynamic and kinetic stability under extreme conditions in combination with the high entropy effect. Therefore, the research, development and application of new catalyst preparation technologies are urgently needed.

[0004] At present, chemical vapor deposition (CVD) and atomic layer deposition (ALD) can also produce high entropy alloy thin film catalysts and multi-metallic ceramic thin film catalysts, but they are extremely inefficient and very expensive. Hydrothermal, sol-gel, and electrochemical methods can also produce high entropy alloy thin film catalysts, but they are subject to serious pollution, high costs, and low catalyst adhesion. Carbon thermal shock can also produce high entropy alloy thin film catalysts and multi-metallic ceramic thin film catalysts, but they still have the disadvantages of needing to use liquid precursors, only conductive supports can be selected as supports, and the control over the morphology of high entropy nanoalloys is lower than that of the method of the present invention. Summary of the Invention [Problem to be solved by the invention]

[0005] In response to the above technical problems, the present invention provides a manufacturing apparatus and method for thin film catalysts to solve the problems of the prior art, such as low manufacturing efficiency of medium and high entropy alloy thin films and multi-metal element ceramic thin film catalysts, long film formation times, high costs, serious pollution, and the inability to be used for large-scale industrial production. [Means for solving the problem]

[0006] In order to achieve the above object, the present invention provides: A vacuum chamber for creating a vacuum environment; a plurality of evaporators provided in the vacuum chamber for evaporating at least one film forming material; a plurality of gas introduction tubes provided in the vacuum chamber for supplying a reaction gas; an ion generator provided in the vacuum chamber for ionizing the reactive gas and the evaporated film forming material; and a control unit connected to the vacuum chamber, the plurality of evaporators, the plurality of gas introduction tubes, and the ion generator, for controlling the vacuum chamber to perform vacuum suction, for starting at least two of the plurality of evaporators, for controlling the gas introduction tubes to supply reactive gases, and for controlling and adjusting a magnitude of an ion source current of the ion generator so that the evaporated film forming material reacts with the reactive gas to deposit a catalyst film on the surface of a substrate.

[0007] In a preferred technical form, the plurality of evaporators comprises at least one first evaporator and at least one second evaporator, the first evaporator being an electron beam or laser evaporator and the second evaporator being a resistive evaporator.

[0008] In a preferred technical form, the thin film catalyst is a medium to high entropy alloy thin film catalyst or a high entropy ceramic thin film catalyst, or a multi-metallic element ceramic thin film catalyst.

[0009] As a preferred technical form, the apparatus further includes a winding mechanism that is rotatably provided within the vacuum chamber and drives the substrate to rotate.

[0010] As a preferred technical form, the present invention further includes a rotating means, the rotating means including a motor, an orbital disk, a first support ring, a second support ring, a rotating disk holder, and a winding mechanism holder, the orbital disk, the first support ring, and the second support ring are arranged in parallel, the output shaft of the motor is connected to a central axis of the orbital disk, the winding mechanism is movably fixed to the winding mechanism holder, the winding mechanism holder is arranged between the first support ring and the second support ring, both ends of the winding mechanism holder are connected to the first support ring and the second support ring, respectively, both ends of the rotating disk holder are connected to the orbital disk and the first support ring, respectively, and the motor drives the orbital disk to rotate, thereby rotating the winding mechanism holder and rotating the winding mechanism.

[0011] As a preferred technical embodiment, the device further includes a bias negative voltage device that is provided in the vacuum chamber and may be a preferred technical embodiment, where the bias negative voltage is U, and −380v≦U<0v.

[0012] A preferred technical form further includes a cold trap system and a heating system provided within the vacuum chamber.

[0013] In a preferred technical form, the ion source of the ion generator is a Hall ion source.

[0014] The present invention also provides Step S1 of performing vacuum suction; Step S2 of activating the ion generator with an ion source current at a first current to purge the substrate; and step S3 of maintaining the ion source current at the first current, introducing a first reactant gas and activating a plurality of evaporators to deposit a first catalyst film layer on the substrate, the first catalyst film layer being a compound of a metal or a plurality of compounds of a metal or a composite of compounds of a plurality of metals, wherein the compound of the first catalyst film layer is an oxide, a nitride, a carbide, a sulfide, a boride, or a complex.

[0015] In a preferred technical form, the plurality of evaporators comprises at least one first evaporator and at least one second evaporator, the first evaporator being an electron beam or laser evaporator and the second evaporator being a resistive evaporator.

[0016] As a preferred technical form, after step S3, Step S4 of adjusting the ion source current to a second current smaller than the first current, introducing a second reactive gas, and depositing a second catalyst film layer on the first catalyst film layer, the second catalyst film layer being a compound of a metal, a plurality of compounds of a metal, or a composite of compounds of a plurality of metals, the compound of the second catalyst film layer being an oxide, a nitride, a carbide, a sulfide, a boride, or a complex; The method further includes a step S5 of repeating the steps S3 and S4 in sequence according to a preset number of layers, and setting the ion source current used when manufacturing the outermost catalyst film remote from the substrate to the first current.

[0017] In a preferred technical embodiment, the first and second reaction gases are each one selected from oxygen gas, nitrogen gas, and methane.

[0018] In a preferred technical embodiment, the first catalyst membrane layer and the second catalyst membrane layer are both metal oxides, and the second current is zero.

[0019] In a preferred technical embodiment, the first current is 5A to 10A, and the second current is 0A to 5A.

[0020] In a preferred technical embodiment, the deposition time of the first catalyst membrane layer and the deposition time of the second catalyst membrane layer are both 5 minutes or less.

[0021] In a preferred technical form, argon gas is also introduced in step S2.

[0022] As a preferred technical embodiment, the amount of argon gas introduced in step S3 is the same as that in step S4.

[0023] In a preferred technical embodiment, the second catalyst membrane layer has a thickness of 5 to 30 nm.

[0024] In a preferred technical embodiment, the first catalyst membrane layer has a thickness of 5 to 30 nm.

[0025] In a preferred technical embodiment, step S3 further includes supplying a negative bias voltage to form an electric field, where U is the negative bias voltage and −380v≦U<0v.

[0026] In a preferred technical embodiment, the deposition time of the first catalyst membrane layer is 2 to 3 minutes.

[0027] In a preferred technical embodiment, when the first current is 0 to 5 A, the specific surface area of ​​the first catalyst membrane layer is 20 to 200 m 2 / g, and when the first current is 5 to 10 A, the specific surface area of ​​the first catalyst membrane layer is 0.2 to 20 m 2 / g Effect of the Invention

[0028] Compared with the prior art, the above technical aspects of the present invention have the following advantages: (1) The present invention adopts a co-deposition ion reaction method using a multiple radiation source combined with an ionization mixing method of an ion source and argon gas, which not only solves the problem of poor high temperature resistance of non-co-deposition film catalysts, but also allows various element ions in the vacuum chamber to collide with each other through the cooperation of the ion source and the accelerated impact of argon ions, causing ion reactions, and the reaction products are rapidly deposited on the target substrate to form sub-nanometer or nanometer order amorphous and crystalline thin films. (2) In the present invention, the speed at which the film-forming material is excited to generate ions is high, the reaction rate between ions is fast, and the film can be formed instantly in a short time. This breaks the conventional wisdom that film-forming time is measured in hours, and the present invention makes it possible to carry out multi-metal element ion reactions quickly and on a large scale, and to produce medium and high entropy alloy thin films and multi-metal element ceramic thin film catalysts, laying the foundation for large-scale industrial production. (3) In the present invention, a negative bias voltage is also applied on the substrate in the vacuum chamber to promote the deposition of ions or compounds, allowing the ionic reaction to continue on the primary film, thereby producing more high-entropy alloys or complexes and improving the stability of the catalytic active sites, especially the stability at high temperatures. The laminated thin film catalyst produced by this method is a non-van der Waals force two-dimensional film, with high binding force and stable active sites. (4) The manufacturing system of the present invention requires inexpensive raw materials, and the cost of raw materials (film-forming materials) is significantly reduced compared to magnetron sputtering targets. In addition, the manufacturing process of the present invention does not produce any acid, alkali, or solid / liquid waste, and the small amount of vacuum exhaust gas meets the standards with just a simple gas filter, making it an environmentally friendly manufacturing method. Furthermore, the manufacturing process of the present invention is highly reliable and stable. In order to more clearly describe the specific embodiments of the present invention or the technical solutions of the prior art, the following briefly describes the drawings that need to be used to describe the specific embodiments or the prior art. The drawings described in the following description are only some embodiments of the present invention, and it is obvious that those skilled in the art can obtain other drawings from these drawings without creative efforts. [Brief description of the drawings]

[0029] [Figure 1] 1 is a schematic diagram of a thin film catalyst manufacturing apparatus according to one embodiment of the present invention. [Diagram 2] 1 is a schematic diagram of a group of radiation sources and ion sources of a thin film catalyst manufacturing apparatus according to one embodiment of the present invention. [Diagram 3] 1 is a schematic flow diagram of a method for producing a thin film catalyst according to an embodiment of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0030] In order to allow a further understanding of the object, structure, features, and functions of the present invention, a detailed description will be given below with reference to examples. Note that the orientation or positional relationship indicated by terms such as "upper", "lower", "left", and "right" is based on the orientation or positional relationship shown in the drawings, and the shape, size, orientation, or positional relationship of each element shown in the drawings is merely for facilitating the description of the technical contents of the present invention, and is not to be understood as limiting the present invention.

[0031] Referring to FIG. 1 and FIG. 2, FIG. 1 is a schematic diagram of a manufacturing apparatus for a thin film catalyst according to an embodiment of the present invention, and FIG. 2 is a schematic diagram of a radiation source and an ion source group of the manufacturing apparatus for a thin film catalyst according to an embodiment of the present invention. The present invention provides a manufacturing apparatus for a thin film catalyst, for example, a medium-high entropy alloy thin film catalyst, a high entropy alloy ceramic thin film catalyst, or a multi-metal element ceramic thin film catalyst, and the metal element ceramic means an oxide, nitride, carbide, sulfide, boride, and mixtures and compounds (complexes) of metal elements. High-entropy alloys are abbreviated as HEA, and are alloys formed of equal or nearly equal amounts of five or more metals. Medium-entropy alloys are a concept developed based on high-entropy alloys, and their main elements are ternary single-phase alloys. High-entropy ceramics are abbreviated as HEC, and are made of a multi-element solid solution inorganic material in which the occupancies of elements including one or more types of Wyckoff sites are the same or similar (5 to 35%).

[0032] The thin film catalyst manufacturing apparatus includes a vacuum chamber 1, a plurality of evaporators 2, a plurality of gas introduction tubes 3, an ion generator 4, and a control unit 20. The vacuum chamber 1 creates a vacuum environment. The plurality of evaporators 2 are provided in the vacuum chamber 1 to evaporate at least one film-forming material, and the evaporator 2 evaporates the film-forming material and converts it into an atomic group, an ion source, and a partial (insufficient) ion state. In actual production, desired film-forming materials are respectively loaded into these evaporators, and according to actual needs, such film-forming materials may be the same or different. The plurality of gas introduction tubes 3 are provided in the vacuum chamber 1 to supply reactive gases, where the reactive gas may be determined according to the components of the film-forming material, and may be, for example, oxygen gas, nitrogen gas, argon gas, or methane. The ion generator 4 is provided in the vacuum chamber 1 to ionize the reactive gases and the film-forming material after evaporation. The control unit 20 is connected to the vacuum chamber 1, the plurality of evaporators 2, the plurality of gas introduction tubes 3, and the ion generator 4. For example, the control unit 20 can control the degree of vacuum and temperature in the vacuum chamber, and the current and speed of the evaporator 2 and the ion generator 4.

[0033] The control unit 20 also controls the vacuum chamber 1 to perform vacuum suction, starts at least two of the multiple evaporators 2, controls the gas introduction tube 3 to supply the reactive gas, and controls and adjusts the magnitude of the ion source current of the ion generator 4 to react the evaporated film forming material with the reactive gas to deposit a catalyst film on the surface of the substrate, thereby producing the thin film catalyst of the present invention. The above catalyst film is, for example, a compound of one metal, multiple compounds of one metal, or a composite of multiple metal compounds, where the compound is an oxide, nitride, carbide, sulfide, boride, or complex, and the above metal is, for example, Ti, V, Cr, Mn, Fe, Co, Ni, and Cu.

[0034] The above-mentioned multiple evaporators 2 include at least one first evaporator 21 and at least one second evaporator 22, the first evaporator 21 is, for example, an electron beam or laser evaporator and is implemented as an electron gun, the electron gun is for evaporating high melting point materials such as ceramics, metal tungsten, molybdenum, or customized high melting point alloy materials, and the second evaporator 22 is a resistive evaporator for evaporating low melting point materials such as tungsten, manganese, cobalt, copper, zinc, etc. In addition, in the present invention, the deposition material used may be a single metal deposition material or a composite deposition material of multiple metals, but may be specifically determined according to actual needs. In addition, as the ion source of the ion generator 4, any form of ion source is possible, but preferably, a hall ion source is used for large-scale production, and a high frequency ion source is used for locally controlling the dispersion of irregular elements or the regular arrangement of crystal phases.

[0035] In addition, the thin film catalyst manufacturing apparatus further includes a winding mechanism 30 that is rotatably installed in the vacuum chamber 1 and drives the substrate to rotate. The winding mechanism 30 is connected to the control unit 20, and the control unit also controls the winding operation of the winding mechanism 30. In this embodiment, the winding mechanism 30 is preferably located on one side of the multiple evaporators 2 to enable the evaporators 2 to evaporate the film-forming material toward the winding mechanism 30, but the present invention is not limited thereto, and the position of the winding mechanism 30 is preferably one that efficiently and uniformly deposits the catalyst film on the surface of the substrate.

[0036] Continuing to refer to FIG. 1, in this embodiment, the thin film catalyst manufacturing apparatus further includes a rotating means, which includes a motor 5, a revolving disk 6, a first support ring 7, a second support ring 8, a rotating disk holder 9, and a winding mechanism holder 10, the revolving disk 6, the first support ring 7, and the second support ring 8 are arranged in parallel, the output shaft 51 of the motor 5 is connected to the central axis of the revolving disk 6, the winding mechanism 30 is movably fixed to the winding mechanism holder 10, the winding mechanism holder 10 is arranged between the first support ring 7 and the second support ring 8, both ends of the winding mechanism holder 10 are connected to the first support ring 7 and the second support ring 8, respectively, both ends of the rotating disk holder 9 are connected to the revolving disk 6 and the first support ring 7, respectively, and the motor 5 rotates the revolving disk 6 to rotate the winding mechanism holder 10, which rotates the winding mechanism 30. Furthermore, preferably, the winding mechanism holder 10 has an integral structure, and the winding mechanism holder 10 and the first support ring 7 are connected by a fixed buckle 11, that is, the winding mechanism holder 10 is locked to the first support ring 7 by the fixed buckle 11, and thus the winding mechanism holder 10 can stably rotate the winding mechanism 30 by rotating the first support ring 7. Also, the rotating disc holder 9 and the first support ring 7 may be connected by, for example, a roller 12, and the winding mechanism holder 10 and the second support ring 8 may be connected by a roller 13.

[0037] Furthermore, each of the winding subsystems of the winding mechanism 30 can revolve and rotate, and when the substrate is fixed to the winding mechanism 30, the distance from the ion source of the ion generator 4 to each lateral portion of the substrate changes uniformly, and theoretically, when converted into one rotation period (one week), the deposition speed and time of the ionized substance in the vacuum chamber onto the substrate are consistent. In addition, the revolution of each of the winding subsystems gives a uniform disturbance to the ionized substance in the vacuum chamber, so that the lateral thickness of the generated film is relatively uniform. Taking a prototype of a vacuum chamber with a diameter of 1.6 m as an example, the error in the thickness between the center and edge of the film in the lateral direction is less than 2.4%, thereby resulting in a high product yield rate. On the other hand, if each of the winding subsystems does not revolve, the lateral thickness of the deposited film will be non-uniform, resulting in poor film quality. Taking a prototype of a vacuum chamber with a diameter of 1.6 m as an example, the error in the thickness between the center and edge of the film in the lateral direction is as high as 26%. The larger the volume of the vacuum chamber, the larger the lateral error of the film and the lower the yield rate of the product.

[0038] Further, in this embodiment, the thin film catalyst manufacturing apparatus further includes a bias negative voltage device 14, which is installed in the vacuum chamber 1, for supplying a bias negative voltage to the substrate to form an electric field in the vacuum chamber 1. Preferably, the above bias negative voltage is U, -380v≦U<0v. A bias negative voltage is applied to the workpiece in the vacuum chamber 1 (becoming negative pole), the potential of the case of the vacuum chamber 1 is 0, and the reactive gas is ionized by the ion source and argon gas, and the reactive gas ions impact the surface of the metal workpiece under the action of the electric field to cause a low-temperature ion reaction with the elements on the surface. That is, the evaporator 2 evaporates the film-forming material to make it into atomic groups, ion sources, and partially (insufficiently) ionized state, and when argon gas is introduced into the vacuum chamber, the ion generator 4 ionizes the argon gas, and the argon ions impact the evaporated film-forming material to further ionize it. The application of an electric field can also fully ionize the argon gas, and the argon ions impact the evaporated film material to further ionize the evaporated film material. The negative pole of the electric field attracts the ions, allowing them to be deposited more quickly. In addition, the electric field also has the following effects: (1) The ions are quickly collided with the surface of the initially generated two-dimensional nano film, and many different ions are inserted into the thin film to form more complex compounds or complexes, increasing the amorphous or crystalline defects, and improving the catalytic effect of the film and the stability of the catalytic active sites, especially the high temperature resistance. (2) The presence of an electric field increases the deposition rate of ions on the substrate, improving the deposition rate. For example, it originally took about 5 minutes to deposit a 30 nm film, but the presence of an electric field increases the deposition rate of ions on the substrate, making it possible to deposit a 30 nm film in 3 minutes.

[0039] In addition, a cold trap system and a heating system are further provided within the vacuum chamber 1, the cold trap system being used for producing an amorphous catalyst film, and the heating system being used for adjusting the temperature within the vacuum chamber 1 and the heating of the film forming material.

[0040] In addition, as shown in FIG. 2, since the multi-radiation source co-deposition ion reaction method is used in the present invention, a plurality of electron beam or laser evaporators 21 and resistance evaporators 22 are provided. In this embodiment, the number of electron beam or laser evaporators 21 and resistance evaporators 22 is three, but the present invention is not limited to this and may be determined according to the actual situation. In addition, in this embodiment, one ion generator 23 and six gas introduction tubes 24 are further provided. Therefore, according to the above-mentioned manufacturing apparatus of the present invention, it is possible to combine co-evaporation of a plurality of materials and multi-ion reactions, and to efficiently synthesize the target product. Specifically, for example, high melting point film forming materials: tungsten W (melting point 3410°C), graphite C (melting point 3850°C), chromium Cr (melting point 1890°C) are placed in the crucible of an electron gun to serve as an electron beam evaporation source, low melting point film forming materials: iron Fe (melting point 1535°C), copper Cu (melting point 1083°C), zinc Zn (melting point 419°C) are placed in a resistance evaporation crucible to serve as a resistance evaporation source, and the deposition speed is set according to the vacuum sound speed of each film forming material, for example, 1.0 angstrom / sec for chromium, 2 angstrom / sec for copper, etc., and the argon gas speed is set to, for example, 80 ml / s, and it takes about 2 to 3 minutes to form a 30 nm film. In this way, a complex carbide catalyst of multiple metal elements can be synthesized, and the film formation time is significantly reduced compared to the manufacturing equipment in the prior art. By introducing nitrogen gas, complex polymetallic carbonitride ceramic membrane catalysts can be synthesized.

[0041] The substrate may be, for example, one or more combinations of zeolites, electrospun nanofibers, glass fibers, ceramic fibers, ceramic foams, and alloy screens.

[0042] In addition, in this embodiment, an example has been described in which one winding mechanism is arranged in the vacuum chamber, but the present invention is not limited to this, and in actual production, multiple winding mechanisms can be arranged as necessary to meet the demands of large-scale production.

[0043] Referring to FIG. 3, FIG. 3 is a schematic flow diagram of a method for producing a thin film catalyst according to one embodiment of the present invention. The present invention also provides a method for producing a thin film catalyst, the method including the following steps S1 to S3. Step S1: Vacuum suction is performed. Step S2: The ion generator is activated with an ion source current of a first current to purge the substrate. Step S3: Maintain the ion source current at the first current, introduce a first reactive gas, and activate multiple evaporators to deposit a first catalyst film layer on the substrate, the first catalyst film layer being a compound of one metal, multiple compounds of one metal, or a composite of compounds of multiple metals, and the compound of the first catalyst film layer is an oxide, nitride, carbide, sulfide, boride, or complex.

[0044] The above-mentioned multiple evaporators include at least one first evaporator and at least one second evaporator, the first evaporator is an electron beam or laser evaporator, and the second evaporator is a resistance evaporator.

[0045] Furthermore, after step S3, the following steps S4 and S5 are further included. Step S4: Adjust the ion source current to a second current smaller than the first current, introduce a second reactive gas, and deposit a second catalyst film layer on the first catalyst film layer, the second catalyst film layer being a compound of one metal, multiple compounds of one metal, or a composite of compounds of multiple metals, where the compound of the second catalyst film layer is an oxide, nitride, carbide, sulfide, boride, or complex. Step S5: Repeat steps S3 and S4 in sequence according to a preset number of layers, and set the ion source current used when manufacturing the outermost catalyst film remote from the substrate to the first current. The preset number of layers refers to the number of catalyst films to be manufactured, and may be set according to actual needs.

[0046] The first and second reaction gases are each one selected from oxygen gas, nitrogen gas, and methane, and the first and second reaction gases may be the same or different.

[0047] Furthermore, in step S2, argon gas is also introduced, for example, 15 to 30 sccm of argon gas is introduced in step S2, where the argon gas may be used as a protective gas or may be ionized and used in the reaction. Preferably, the amount of argon gas introduced in steps S3 and S4 is the same, for example, 8 to 10 sccm.

[0048] In step S2, the reaction gas has a first introduction amount, and in step S3, the reaction gas has a second introduction amount, and the first introduction amount is equal to or less than the second introduction amount. For example, when the reaction gas is oxygen gas, the first introduction amount of oxygen gas is 20-80 sccm, and the second introduction amount is 80-100 sccm. When the reaction gas is nitrogen gas, the first introduction amount of nitrogen gas is 40-80 sccm, and the second introduction amount is 80-100 sccm. When the reaction gas is methane, the first introduction amount of methane is 20-60 sccm, and the second introduction amount is 60-80 sccm. Of course, the present invention is not limited thereto, that is, the first introduction amount may be larger than the second introduction amount, and in actual production, the introduction amounts of different reaction gases are adjusted according to different cost materials required for different thin film catalysts.

[0049] The first current is, for example, 5A-10A, and the second current is, for example, 0A-5A. In the above steps of the present invention, the first catalyst membrane layer manufactured by turning on the ion source or using a high current (for example, 5A-10A) is denser and can guarantee the bonding force between the membrane and the substrate. The second catalyst membrane layer manufactured by turning off the ion source or using a low current (for example, 0A-5A) can guarantee the comparative area, active sites, and catalytic performance of the catalyst membrane. The manufacture of a denser third catalyst membrane layer is to press down the catalyst membrane with a high specific surface area and prevent its peeling, aging, etc. The manufacture of a fourth catalyst membrane layer with a high specific surface area improves the catalytic performance of the entire material. The specific number of layers of the catalyst membrane can be selected according to actual needs, but the outermost catalyst membrane far from the substrate is a dense layer manufactured at a high current with the ion source always turned on, otherwise it is easy to cause the catalyst membrane to fall off or age. Specifically, when the first current is 0 to 5 A, the specific surface area of ​​the first catalyst membrane layer is 20 to 200 m 2 When the first current is 5 to 10 A, the specific surface area of ​​the first catalyst membrane layer is 0.2 to 20 m 2 / g.

[0050] In another embodiment, the first catalyst membrane layer and the second catalyst membrane layer are both metal oxides, and the second current is 0, that is, the ion source current can be turned off when manufacturing the second catalyst membrane layer, thereby ensuring the specific surface area, active sites and catalytic performance of the second catalyst membrane layer.

[0051] Generally, the performance of metal oxides themselves, such as high temperature resistance and compactness, is inferior to that of metal carbon and nitrogen compounds. However, in the present invention, by using ion source assistance (e.g., switching the ion source current or adjusting the magnitude of the ion source current), it is possible to achieve that the produced catalyst has a high specific surface area and maintains good binding force and stability.

[0052] Preferably, the thickness of the first catalyst membrane layer is 5-30 nm, and the thickness of the second catalyst membrane layer is 5-30 nm. However, the present invention is not limited thereto, and the thickness of each of the catalyst membranes manufactured in the present invention may be greater than 30 nm, and may be determined according to actual needs.

[0053] Furthermore, the deposition time for each of the first and second catalyst membrane layers is 5 minutes or less, and preferably, the deposition time for each of the first and second catalyst membrane layers is 2 to 3 minutes.

[0054] The above-mentioned method for producing a thin film catalyst is carried out, for example, by using the above-mentioned thin film catalyst production apparatus.

[0055] In other words, the production of medium to high entropy alloy thin film or multi-metal element ceramic thin film catalyst using the above-mentioned manufacturing method and manufacturing apparatus of the present invention not only is fast, with the film formation time basically being kept within 5 minutes, but also has high film formation quality. With the assistance of adjusting the ion source current, the high temperature resistance and denseness of the metal oxide can be improved, and the overall performance of the thin film catalyst can be improved.

[0056] The present invention will now be further illustrated by the following specific examples.

[0057] Example 1 (1) Vacuum suction was performed in the vacuum chamber. (2) An ion generator with an ion source current of 6 A was started, and the substrate was purged for 60 s with an argon gas introduction rate of 15 sccm. (3) The ion source current was maintained at 6 A, while the argon gas flow rate was reduced to 8 sccm. (4) The electron beam evaporation apparatus and the resistance evaporation apparatus were started, Al and Ti were placed in the crucible of the electron gun, Ce and Fe were placed in the resistance evaporation crucible, oxygen gas was introduced at an input rate of 20 sccm, the electron gun current for the Al2O3 film material was set to 300 mA, the speed was 3.0 angstroms / sec (300 mA, 3.0 angstroms / sec), the electron gun current for the TiO2 film material was set to 140 mA, the speed was 1.0 angstroms / sec (140 mA, 1.0 angstroms / sec), the CeO2 current was set to 50 mA, the speed was 0.5 angstroms / sec (50 mA, 0.5 angstroms / sec), and the Fe current was set to 60 mA, the speed was 0.5 angstroms / sec (60 mA, 0.5 angstroms / sec), and these four materials were evaporated for a total of 100 s to obtain a first catalyst film layer. It took about 4 minutes to deposit a 30 nm film.

[0058] Example 2 (1) Vacuum suction was performed in the vacuum chamber. (2) An ion generator with an ion source current of 6 A was started, and the substrate was purged for 60 s with an argon gas introduction rate of 15 sccm. (3) The ion source current was maintained at 6 A, while the argon gas flow rate was reduced to 8 sccm. (4) The electron beam evaporation apparatus and the resistance evaporation apparatus were started, Al and Ti were placed in the crucible of the electron gun, CeO2 and Fe were placed in the resistance evaporation crucible, oxygen gas was introduced at an input rate of 20 sccm, the electron gun current for the Al2O3 film material was set to 300 mA, the speed was set to 3.0 angstroms / sec (300 mA, 3.0 angstroms / sec), the electron gun current for the TiO2 film material was set to 140 mA, the speed was set to 1.0 angstroms / sec (140 mA, 1.0 angstroms / sec), the CeO2 current was set to 50 mA, the speed was set to 0.5 angstroms / sec (50 mA, 0.5 angstroms / sec), and the Fe current was set to 60 mA, the speed was set to 0.5 angstroms / sec (60 mA, 0.5 angstroms / sec), and these four materials were evaporated for a total of 100 s to obtain a first catalyst film layer. It took about 4 minutes to deposit a 30 nm film. (5) The electron beam evaporator and the resistance evaporator were started, the ion generator was stopped, oxygen gas was introduced at an introduction rate of 80sccm, and the deposition rates were set according to the vacuum sound velocity of each film-forming material to Co (current 190mA, 2 angstroms / sec), Mn (6mA, 0.5 angstroms / sec), W (490mA, 0.2 angstroms / sec), Mo (400mA, 0.3 angstroms / sec), and Cu (300mA, 1.0 angstroms / sec). The five materials were deposited for a total of 100s to obtain a second catalyst film layer. It took about 4 minutes to form a 30nm film. (6) The electron beam evaporator and the resistance evaporator were started, an ion generator with an ion source current of 6A was started, oxygen gas was introduced at an introduction rate of 40sccm, and the deposition rates were set according to the vacuum sound velocity of each film-forming material to Co (current 190mA, 2 angstroms / sec), Mn (6mA, 0.5 angstroms / sec), W (490mA, 0.2 angstroms / sec), Mo (400mA, 0.3 angstroms / sec), and Cu (300mA, 1.0 angstroms / sec). The five materials were deposited for a total of 100s to obtain the third catalyst film layer. It took about 3 minutes to form a 30nm film.

[0059] Example 3 (1) Vacuum suction was performed in the vacuum chamber. (2) An ion generator with an ion source current of 6 A was started, and the substrate was purged for 60 s with an argon gas introduction rate of 15 sccm. (3) The ion source current was maintained at 6 A, while the argon gas flow rate was reduced to 8 sccm. (4) Activate the electron beam evaporation device and the resistance evaporation device, apply a negative bias voltage of -160V, place Al and Ti in the crucible of the electron gun, place CeO2 and Fe in the resistance evaporation crucible, introduce oxygen gas at an introduction rate of 20sccm, set the current of the electron gun for the Al2O3 film material to 300mA, the speed to 3.0 angstroms / sec (300mA, 3.0 angstroms / sec), and the electron gun for the TiO2 film material to 300mA. The four materials were deposited for a total of 100 s with a current of 140 mA and a rate of 1.0 Å / s (140 mA, 1.0 Å / s) for CeO2, a current of 50 mA and a rate of 0.5 Å / s (50 mA, 0.5 Å / s) for Fe, and a current of 60 mA and a rate of 0.5 Å / s (60 mA, 0.5 Å / s) for Fe, to obtain the first catalyst film layer. The time required to deposit a 30 nm film was approximately 3 minutes. (5) The electron beam evaporator and the resistance evaporator were started, the ion generator was stopped, 80V was applied as a bias negative voltage, oxygen gas was introduced at an introduction rate of 80sccm, and the deposition rates were set according to the vacuum sound velocity of each film-forming material to Co (current 190mA, 2 angstroms / sec), Mn (6mA, 0.5 angstroms / sec), W (490mA, 0.2 angstroms / sec), Mo (400mA, 0.3 angstroms / sec), and Cu (300mA, 1.0 angstroms / sec), and the five materials were deposited for a total of 100s to obtain a second catalyst film layer. It took about 3 minutes to form a 30nm film. (6) The electron beam evaporator and the resistance evaporator were started, an ion generator with an ion source current of 6A was started, -220V was applied as a bias negative voltage, oxygen gas was introduced at an introduction rate of 40sccm, and the deposition rates were set according to the vacuum sound velocity of each film-forming material as Co (current 190mA, 2 angstroms / sec), Mn (6mA, 0.5 angstroms / sec), W (490mA, 0.2 angstroms / sec), Mo (400mA, 0.3 angstroms / sec), and Cu (300mA, 1.0 angstroms / sec), and the five materials were deposited for a total of 100s to obtain a third catalyst film layer. It took about 2 minutes to form a 30nm film.

[0060] Example 4 (1) Vacuum suction was performed in the vacuum chamber. (2) An ion generator with an ion source current of 10 A was started, and the substrate was purged for 60 s with an argon gas introduction rate of 24 sccm. (3) The ion source current was maintained at 10 A, while the argon gas flow rate was reduced to 10 sccm. (4) The electron beam evaporator and the resistance evaporation evaporator were started, W and Cr were placed in the crucible of the electron gun, Fe and Cu were placed in the resistance evaporation crucible, nitrogen gas was introduced at an introduction rate of 20sccm, and the deposition rates were set according to the vacuum sound velocity of each film-forming material to W (490mA, 0.2 angstroms / sec), Cr (300mA, 1.0 angstroms / sec), Fe (60mA, 0.5 angstroms / sec), and Cu (300mA, 1.0 angstroms / sec), and these four materials were evaporated for a total of 100s to obtain a first catalyst film layer. It took about 3 minutes to form a 30nm film. (5) The electron beam evaporator and the resistance evaporator were started, the ion source current was adjusted to 5A, nitrogen gas was introduced at an input rate of 100sccm, and the deposition rates were set to Al (300mA, 3.0 angstroms / sec), CeO2 (50mA, 0.5 angstroms / sec), Mo (400mA, 0.3 angstroms / sec), and Cu (300mA, 1.0 angstroms / sec) according to the vacuum sound velocity of each film-forming material, and the five materials were deposited for a total of 100s to obtain a second catalyst film layer. It took about 2 minutes to form a 30nm film. (6) The electron beam evaporator and the resistance evaporator were started, the ion source current was adjusted to 10A, nitrogen gas was introduced at an input rate of 80sccm, and the deposition rates were set to W (490mA, 0.2 angstroms / sec), Cr (300mA, 1.0 angstroms / sec), Fe (60mA, 0.5 angstroms / sec), Cu (300mA, 1.0 angstroms / sec), and CeO2 (50mA, 0.5 angstroms / sec) according to the vacuum sound velocity of each film-forming material, and the five materials were deposited for a total of 100s to obtain the third catalyst film layer. It took about 2 minutes to form a 30nm film.

[0061] Example 5 High entropy two-dimensional film CuFeNiMoCoTi

[0062] Mo and Ti were placed in the crucible of an electron gun, and Cu, Fe, Ni, and Co were placed in a resistance evaporation crucible. The deposition rate was set according to the vacuum sound velocity of each film-forming material, for example, 0.5 angstroms / second for tungsten and 2 angstroms / second for iron, and it took about 2 minutes to form a 30 nm film.

[0063] Example 6 High entropy two-dimensional film CrMoNiMnVWZn Mo, V, W, Ti, and Cr were placed in the crucible of the electron gun, and Mn, Ni, and Zn were placed in the resistance evaporation crucible. The deposition rate was set according to the vacuum sound velocity of each film-forming material, for example, 1.0 angstrom / sec for molybdenum and 3 angstroms / sec for iron, and it took about 3 minutes to form a 50 nm film.

[0064] Example 7 Multi-metal element ceramic two-dimensional film FeCrWCuN W and Cr were placed in the crucible of an electron gun, Fe and Cu were placed in a resistance evaporation crucible, and nitrogen gas was introduced. The deposition rate was set according to the vacuum sound velocity of each film-forming material, for example, 1.0 angstrom / sec for chromium and 2 angstrom / sec for copper, and the nitrogen gas rate was set to, for example, 80 ml / s. It took about 2 to 3 minutes to form a 30 nm film.

[0065] Example 8 Multi-metal element ceramic two-dimensional film AlCeCoZrMnO Zr and CeO were placed in the crucible of an electron gun, and Al, Co, and Mn were placed in a resistance evaporation crucible. Oxygen gas was introduced as the gas. Depending on the vacuum sound velocity of each film-forming material, the deposition rate was set to, for example, 1.0 angstrom / sec for zirconium and 2.5 angstrom / sec for manganese, and the oxygen gas rate was set to, for example, 60 ml / s. It took about 2 to 3 minutes to form a 40 nm film.

[0066] Example 9 When a nitrogen ceramic film obtained by co-evaporating six elements, Al, Ce, Mo, Co, Zr, and Fe, is treated at 240°C to 250°C, it has excellent effect on dimethylacetamide VOC, which is converted into water, carbon dioxide, and nitrogen gas by the catalyst.

[0067] Example 10 The Cu-based three-metal element oxide ceramic thin film catalyst, based on nonwoven fabric and stainless steel mesh, has a killing efficiency of over 98.8% against the H1N1 coronavirus in one minute and a virus killing efficiency of over 99% in 10 minutes.

[0068] From Examples 1 to 8, it was found that when using the medium to high entropy alloy thin film or multi-metal element ceramic thin film catalyst produced by the manufacturing method of the present invention, the deposition rate was fast and the time required to form a 30 nm film was reduced to approximately 2 to 3 minutes.

[0069] The experimental conditions were the same in Example 2 and Example 3, except that a negative bias voltage was applied in Example 3. It was found that the film formation time in Example 3 was significantly shortened.

[0070] In Example 9, the nitrided ceramic membrane produced by the manufacturing method of the present invention has an excellent effect of treating dimethylacetamide VOC at 240°C to 250°C, but in the prior art, in order to achieve the same efficiency as the multimetallic ceramic thin film catalyst produced by the present invention, the nitrogen-containing VOC catalyst produced by the immersion method or the saturated coprecipitation method needs to increase the operating temperature by 150 to 250°C or reduce the VOC speed passing through the catalyst to 1.6 cm / s. On the other hand, the wind speed of the thin film catalyst of the present invention is 20 cm / s (the wind speed after treatment can be 1 to 7 m / s according to industrial needs). Compared with the hydrothermal method, in order to produce a cobalt nitride catalyst with high binding strength and high dispersion, magnesium hydroxide is used as a template agent, and cobalt acetate and phenanthroline (nitrogen source) are used as precursors, reacted at 200°C, and then the magnesium hydroxide template agent is removed by acid washing. Compared with the manufacturing method of the present invention, this method has a step of introducing impurities, and the accuracy is not comparable to the deposition method or sputtering method. By using this manufacturing method to industrially produce multimetal element ceramic thin film catalysts, it is possible to reduce investment to 1 / 3 to 1 / 2 compared to conventional facilities for treating such VOCs, and there is no need to consume large amounts of natural gas during operation, and the electric energy required for heating can be significantly reduced, resulting in lower running costs.

[0071] In Example 10, the multi-metal ceramic thin film catalyst was grown in situ on nonwoven fabric and stainless steel wire mesh to produce a product for eliminating coronavirus, and good results were obtained. By using this manufacturing method to industrially produce the multi-metal ceramic thin film catalyst, the multi-metal ceramic thin film catalyst can be widely used in the rapid elimination of coronavirus in the environmental protection field, medical hygiene systems, central air conditioning systems in buildings such as CBDs, and air purification systems in enclosed spaces such as high-speed trains and aircraft.

[0072] As described above, the present invention adopts the co-deposition ion reaction method using multiple radiation sources combined with the ionization mixing method of the ion source and argon gas, which not only solves the problem of poor high temperature resistance of non-co-deposition film catalysts, but also allows various element ions in the vacuum chamber to collide with each other through the cooperation of the ion source and the accelerated impact of argon ions, causing ion reactions, and the reaction products can be rapidly deposited on the target substrate to form sub-nanometer order or nanometer order amorphous and crystalline thin films. In addition, the film material can be excited to generate ions at a fast rate, the reaction rate between ions is fast, the film can be formed instantly in a short time, and the multi-metal element ion reaction can be carried out quickly and on a large scale to produce medium and high entropy alloy thin films and multi-metal element ceramic thin film catalysts, which can lay the foundation for large-scale industrial production. In the present invention, a bias negative voltage is also applied on the substrate in the vacuum chamber to promote the deposition of ions or compounds, allowing the ion reaction to continue on the primary film, thereby generating more high entropy alloys or complexes and improving the stability of the catalytic active sites, especially their stability at high temperatures. Furthermore, the manufacturing system of the present invention requires inexpensive raw materials, and the cost of raw materials (film-forming materials) is significantly reduced compared to magnetron sputtering targets. The manufacturing process of the present invention does not produce any acid, alkali, or solid / liquid waste, and the small amount of vacuum exhaust gas meets the standards with just a simple gas filter, making it an environmentally friendly manufacturing method. Furthermore, the manufacturing process of the present invention is highly reliable and stable.

[0073] The present invention has been described by the above related examples, but the above examples are merely examples for implementing the present invention. In addition, the technical features according to each embodiment of the present invention may be combined with each other as long as they are not mutually inconsistent. The disclosed examples do not limit the scope of the present invention. Meanwhile, any changes and modifications made within the scope of the spirit and scope of the present invention are within the scope of patent protection of the present invention.

Claims

1. An apparatus for producing a thin film catalyst, comprising: A vacuum chamber for creating a vacuum environment; a plurality of evaporators provided in the vacuum chamber for evaporating at least one film forming material; a plurality of gas introduction tubes provided in the vacuum chamber for supplying a reaction gas; an ion generator provided in the vacuum chamber for ionizing the reactive gas and the evaporated film forming material; a control unit connected to the vacuum chamber, the plurality of evaporators, the plurality of gas introduction tubes, and the ion generator, for controlling the vacuum chamber to perform vacuum suction, for starting at least two of the plurality of evaporators, for controlling the gas introduction tubes to supply reactive gases, and for controlling and adjusting a magnitude of an ion source current of the ion generator so that the evaporated film forming material reacts with the reactive gas to deposit a catalyst film on a surface of a substrate; a winding mechanism rotatably provided in the vacuum chamber for rotating the substrate; and a pivot means, the rotating means includes a motor, an orbital disk, a first support ring, a second support ring, a rotating disk holder, and a winding mechanism holder, the orbital disk, the first support ring, and the second support ring are arranged in parallel, the output shaft of the motor is connected to a central axis of the orbital disk, the winding mechanism is movably fixed to the winding mechanism holder, the winding mechanism holder is arranged between the first support ring and the second support ring, both ends of the winding mechanism holder are connected to the first support ring and the second support ring, respectively, and both ends of the rotating disk holder are connected to the orbital disk and the first support ring,

2. 2. The thin film catalyst manufacturing apparatus of claim 1, wherein the plurality of evaporators include at least one first evaporator and at least one second evaporator, the first evaporator being an electron beam or laser evaporator, and the second evaporator being a resistance evaporator.

3. 2. The apparatus for producing a thin film catalyst according to claim 1, wherein the thin film catalyst is a multi-metallic element ceramic thin film catalyst.

4. 2. The apparatus for manufacturing a thin film catalyst according to claim 1, further comprising a bias negative voltage device provided in the vacuum chamber for supplying a bias negative voltage to generate an electric field in the vacuum chamber.

5. 5. The thin film catalyst manufacturing apparatus according to claim 4, wherein the negative bias voltage is U, and the voltage satisfies -380v≦U<0v.

6. 2. The apparatus for producing a thin film catalyst according to claim 1, further comprising a cold trap system and a heating system installed in the vacuum chamber.

7. 2. The apparatus for producing a thin film catalyst according to claim 1, wherein the ion source of the ion generator is a hole ion source.

8. A method for producing a thin film catalyst using the production apparatus according to any one of claims 1 to 7, comprising the steps of: Step S1 of performing vacuum suction; Step S2: activating the ion generator with an ion source current at a first current to purge the substrate; and step S3, maintaining the ion source current at the first current, introducing a first reactant gas and activating a plurality of evaporators to deposit a first catalyst film layer on the substrate, the first catalyst film layer being a compound of a metal or a plurality of compounds of a metal or a composite of compounds of a plurality of metals, the compound of the first catalyst film layer being an oxide, a nitride, a carbide, a sulfide, a boride, or a complex.

9. 9. The method for producing a thin film catalyst according to claim 8, wherein the plurality of evaporators include at least one first evaporator and at least one second evaporator, the first evaporator being an electron beam or laser evaporator, and the second evaporator being a resistive evaporator.

10. After step S3, Step S4: adjusting the ion source current to a second current less than the first current, introducing a second reactive gas, and depositing a second catalyst film layer on the first catalyst film layer, the second catalyst film layer being a compound of a metal, a plurality of compounds of a metal, or a composite of compounds of a plurality of metals, the compound of the second catalyst film layer being an oxide, a nitride, a carbide, a sulfide, a boride, or a complex; 9. The method for producing a thin film catalyst according to claim 8, further comprising a step S5 of repeating the steps S3 and S4 in sequence according to a preset number of layers, and setting the ion source current used when producing an outermost catalyst film remote from the substrate to the first current.

11. 11. The method for producing a thin film catalyst according to claim 10, wherein the first reaction gas and the second reaction gas are each one selected from the group consisting of oxygen gas, nitrogen gas, and methane.

12. 11. The method of claim 10, wherein the first catalyst membrane layer and the second catalyst membrane layer are both metal oxides, and the second current is zero.

13. 11. The method for producing a thin film catalyst according to claim 10, wherein the first current is 5A to 10A, and the second current is 0A to 5A.

14. 11. The method for producing a thin film catalyst according to claim 10, wherein the deposition time of the first catalyst membrane layer and the deposition time of the second catalyst membrane layer are both 5 minutes or less.

15. 11. The method for producing a thin film catalyst according to claim 10, wherein argon gas is also introduced in step S2.

16. 16. The method for producing a thin film catalyst according to claim 15, wherein the amount of the argon gas introduced in step S3 is the same as that in step S4.

17. The method for producing a thin film catalyst according to claim 10, wherein the second catalyst film layer has a thickness of 5 to 30 nm.

18. 18. The method for producing a thin film catalyst according to claim 8 or 17, wherein the first catalyst film layer has a thickness of 5 to 30 nm.

19. 9. The method for producing a thin film catalyst according to claim 8, wherein the step S3 further comprises: supplying a negative bias voltage to form an electric field, where U is the negative bias voltage, and −380v≦U<0v.

20. 20. The method for producing a thin film catalyst according to claim 19, wherein the deposition time of the first catalyst film layer is 2 to 3 minutes.

21. When the first current is 0 to 5 A, the specific surface area of ​​the first catalyst membrane layer is 20 to 200 m ２ / g, and when the first current is 5 to 10 A, the specific surface area of ​​the first catalyst membrane layer is 0.2 to 20 m ２ The method for producing a thin film catalyst according to claim 8, characterized in that the average molecular weight of the catalyst is 1.0 to 1.0 g.

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